Dyestuffs containing chromium and process for manufacture of same



25 agents yiel Patented Mar. 25, i924.-

UNITED STATES PATENT OFFICE.

FRITZ STRAUB, OF BASEL, AND HERMANN SCHNEIDER, OF RIEHEN, NEAR BASEL, SWITZERLAND, ASSIGNO'RS TO SOCIETY OF CHEMICAL INDUSTRY IN BASLE, OF

BASEL, SWITZERLAND.

DYESTUFFS CONTAJiTING CHROMIUM AND PROOF-SS FOR MANUFACTURE OF SAME.

No Drawing.

tion.

This invention relates to new dyestuffs containing chromium which are, valuable acid dyestuffs, and to a process for manufacturing same. The invention comprlses,

besides the dyestuffs and their manufacturing processes, also the fibers dyed with these dyestufis.

It has been found that valuable new dyestuifs containing chromium may be obtained by coupling the l-oxynaphthalene-8-sulfam ide with the diazo-compounds which are derived from the ortho aminonaphthols, their substitution products and their derivatives, and treatingthe dyestufl's thus obtained with ing chromium. I

The dyestuffs thus obtained are therefore derivatives of the aim dyestuffs which correspond with the general formula:

' (wherein R signifies an oxynaphthalene nucleus in which the azo-bridge adheres to an ortho-position in respect of the hydroxylgroup) forming bronze powders whlch dis-- solve in pure water to blue to green black solutionswhich change towards violet to Example 1.

22.3 parts of l-oxynaphthalene-S-sulfamide dissolved cold in an excess of aqueous caustic alkali solution are mixed with 27.2 parts of sodium1-diazo-2-oxynaphthalenetated by addition of common salt.

Application filed October 18, 1923. Serial N0. 669,402.

4-sulfonate. When the coupling, which imare introduced into a boiling mixture of 224 parts of potassium hydroxide, 8.36 parts of chromium oxide, 9 parts of glycerine and 130 parts of water and the mixture is boiled for a long time in a reflux apparatus. The mixture is then diluted with 300 parts of water' made neutral with hydrochloric acid and the new chromium compound precipi- When dried the chromium compound is a bronze powder which dyes wool in an acid bath very equal fast blue tints.

. A chromium compound'which is quite simlar'is produced when the alkaline chroming 1s carried out as prescribed in U. S. patent specification 1,221,849 and patent application Serial No. 539,7 39'.

Example 2.

24.0 parts of the azo-dyestufl as obtained in the preceding example are dissolved in 500 parts of boiling water and the solution is mixed with a chromium formate solution corresponding with 9.5 part of Cr O The mixture is boiled for 24 hours in a reflux apparatus. The solution thus obtained is in part evaporated; on cooling the new chromium compound separates in the form of lustrous crystals. This chromium compound dissolves in pure Water to a blue solution; in dilute caustic soda lye to a violet solution. It dyes wool in an acld bath very uniform fast and pure greenish blue tints.

If chromium fluoride or chromium acetate be substituted for chromium formate, the chromium compounds formed also dye wool fast and equal blue tints.

The chromium compounds of the dyestuffs obtained in like manner from l-oxy- 'naphthalene-S-sulfamide and the haloge- E mample 3.

22.3 parts of l-oxynaphthalene-S-sulfamide dissolved cold in an excess of aqueous caustic alkali solution are mixed at 10 C. with 29.5 parts of nitrated Ld1azo-2-oxynaphthalene--sulfonic acid. Coupling begins at once. When the diazo-compound has disappeared the product of reaction is made neutral with dilute hydrochloric acid and the dyestuif which separates i filtered. The-.dyestufi' thus obtained is a dark powder soluble in pure water and in dilute caustlc soda lye to a red violet solution and in concentrated sulfuric acid to a dark blue solution. It dyes wool in an acid bath black violet, changed towards black when afterchromed.

26 parts of the dyestufi' thus obtained are dissolved in 500 parts of boiling water..

The solution is mixed with a solution of chromium fluoride corresponding with 9.5 parts of Cr O and the mixture is. boiled for 24 hours in a reflux apparatus, if necessary with addition of glass. The solution is then partly evaporated and the chromium compound which has been formed is separated by alting out. It forms a powder having a bronze lustre; dissolves in ure water to a greenish black solution an in dilute caustic soda lye to a violet black solution. It dyes wool in an acid bath fast black tints.

When another 9. nt adapted to ield chromium, such as reshly precipitate hydrated chromium hydroxide, is usedinstead Of chromium fluoride, chromium compounds are also obtained which dye wool fast black tints.

The chromium compound of the dyestufi obtained in like manner from l-oxynaphthalene-8-sulfamide and the diazo-compound of- 1-oxy-2-amino-4-nitronaphthalene-7-sulfonic acid also dyes wool black.

What we claim is:

1. The herein described process for the 'manufacture of new dyestufls containing chromium, which consists in coupling the 1- oxynaphthalene-S-sulfamide with diazocompounds derived from the ortho-aminonaphthols, and treating the dyestuffs thus obtained with agents yielding chromium.

2. The herein described process for the 'manufacture of new dyestuffs containing chromium, which consists in coupling the 1- oxynaphthalene-8-sulfamide with diazocompounds derived from the 1-amino-2-oxynaphthalene--sulfonic acid, and treating the 1 ,eeaeni dyestufi's thus obtained with agents yielding chromium.

3. The herein described process for the manufacture of new dyestuffs containing chromium, which consists in coupling the '7 "l-oxynaphthalene-8-sulfamide with the diwherein R signifies a naphthalene nucleus in which the azo-bridge adheres to an orthoposition in respect of the hydroxyl-group, which dyestufi's form bronze powders soluble in pure water to a blue to green black solution and in dilute caustic alkalies to a blue violet to black violet solution, dyein wool in an acid bath blue to green blue an green black tints of excellent uniformity, prominent fastness to light, and very good fastness to fulling.

5. As new products the herein described new dyestuffs containing chromium which are derivatives of the azo d estufl's which correspond with thegeneral formula:

wherein R signifies a sulfonated naphthalene nucleus in which the azo-brid e adheres to an ortho-position in respect of 5m h droxyl-group, which dyestufi's form ronze powders soluble in pure water to a blue' to green black solution. and in dilute caustic alkalies to a blue violet to black violet solution, dyeing wool in an acid bath blue to green blue and green black tints of excellent uniformity, prominent fastness to light, and very good fastness to 'fulling.

p 6. As new products the herein described new dyestufis containing chromium which are derivatives of the azo dyestuffs which correspond with the general formula:

NHaSOa 0H wherein R signifies a, 2-oxynaphthalenesulfonic acid nucleus in which the azo-bridge adheres to position-1 of the naphthalene nucleus, which dyestuffs form bronze powders soluble in pure water to a blue to green black solution and in dilute caustic alkalies to a blue violet to black violet solution, dyeing wool in an acid vbath blue to green blue and green black tints of excellent uniformity, prominent fastness to light, and

very good fastness to fulling.

7 Ks new products the herein described new dyestufl's containing chromium which are derivatives of the azo dyestufi's which correspond with the general formula:

NHgSO:

wherein R signifies a 2-oxynaphthalene-4- sulfonic acid nucleus in which the ambridge adheres to position-1 of the naphthalene nucleus, which dyestufi's form bronze powders soluble in pure water to a blue to green black solution and in dilute caustic alkalies to a blue violet to black violet solution, dyeing wool in an acid bath blue to green .blue and green black tints of excellent uniformity, prominent fastness to light, and very good fastness to fulling.

8. As a new product the herein described new dyestufi containing chromium which which forms a bronze powder soluble in pure water to a blue to green black solution and in dilute caustic alkalies to a blue violet solution, dyeing wool in an acid bath blue to green blue tints of excellent uniformity, prominent fastness to light, and very good fastness to falling.

9. Material dyed with the 'dyestufis of claim 4.

10 Material dyed with the dyestufi's of claim 5.

11. Material dyed with the dyestufi's of claim 6. Y

12. Material dyed with the dyestufis of claim 7.

13. Material dyed with the dyestuffs of claim 8.

In witness whereof We have hereunto signed our names this 8th day of October, 1923, in the presence of two subscribing witnesses.

FRITZ STRAUB. HERMANN SCHNEIDER. Witnesses:

ARMAND 'BRAUN, LUCIEN PICARD. 

